Diphenyloxide sulfone sulfonic acids



United States Patent US. Cl. 260-512 3 Claims ABSTRACT OF THE DISCLOSURELevelling agents for dyeing anionic dyestuffs are constituted bydiphenylene oxide sulphones, hydroxydiphenylene oxide sulphones,diphenyl oxide sulphones, diphenyl sulphide sulphones, mixtures of thesewith sulphonated aromatic hydrocarbon oils, their alkali metal andammonium salts and/or condensation products, and reaction products ofthese sulphones with formaldehyde or dimethylol urea; an example ofdyeing with such a levelling agent is also given. The use of theselevelling agents avoids stripy or ringy appearance of certain nylonyarns, especially when these are mixed with spandex type fibres.

BACKGROUND OF THE INVENTION Polyamide fibres can be dyed With anionicdyestulfs, but frequently the resulting dyed goods have a stripy orringy appearance due to an uneven adsorption and distribution of dye.Furthermore, mixtures of polyamide fibres and elastomeric polyurethanefibres or yams as are used for making Woven or knitted fabrics cannoteasily be level dyed in equal colour shades with anionic dyestuffs asthese are preferentially adsorbed on the polyamide fibres, thus leavingthe polyurethane fibres in a much paler shade and causing the fabrics tobe stripy.

It has previously been proposed to use certain levelling agents tominimize the above difliculties, but these previously proposed levellingagents have not been entirely satisfactory for one or more of thefollowing reasons: insufficient penetration power, necessity to effect arelatively troublesome separate treatment before dyeing, relatively highprice of the levelling agent, and difiiculties in handling these due totheir being non-solids at ambient temperature.

We have now found that the use of certain novel levelling agentsdescribed hereinafter and which have an excellent penetration powerenables one to dispense with a separate pretreatment before dyeing andto use relatively inexpensive products which, moreover, can -be handledvery easily because they are obtainable in the solid state at roomtemperature.

SUMMARY OF THE INVENTION The present invention provides sulphones of thefor- I 1) wherein m represents 1 or 2,

n represents 1, 2 or 3,

A and A are identical with or different from one another ice and eachrepresents the radical of a compound of the formula wherein each of Zand Z represents a hydrogen atom or Z together with Z represents asingle bond,

and each of Z and Z represents hydrogen, halogen, lower alkyl or alkoxy,hydroxy, carboxy or optionally substituted phenyl,

and each of p and q represents 1 or 2,

and their water soluble salts and quaternary onium compounds, andreaction products thereof resulting by aftersulphonation, treatment withformaldehyde or a methylolradical containing connecting agent, and theneutralized products resulting by neutralizing said reaction productswith a base or an acid.

The present invention also provides a process for the production of theabove sulphones (I), which is characterized in that a compound of theFormula II or a mixture of two or more such compounds is treated with asulphonating agent until the resulting condensation product contains atleast one sulphur atom in the form of a sulphonyl radical and at leastone in the form of a sulphonic acid radical.

DESCRIPTION OF PREFERRED EMBODIMENTS Suitable compounds of the FormulaII are, for example, phenoxybenzene, phenyl thiobenzene and theirderivatives containing 1 to 4 substituents, for instance halogen atoms(e.g. chlorine atoms), lower alkyl or alkoxy radicals (e.g. methyl,ethyl, methoxy, ethoxy) or hydroxy or carboxy radicals; further examplesof compounds of Formula II are 4- or 3-phenoxy-diphenyl, di-benzofuranand 3-hydroxy-dibenzofuran.

Compounds of the Formula II may be used individ ally or in admixturewith one another. However, it is likewise possible to use a mixtureconsisting of one or more compounds of the Formula II and one or morearomatic hydrocarbons which may optionally be substituted with one ormore halogen atoms, alkoxy or hydroxy radicals, providing that themixture has a content of one or more compounds of Formula II of at least30%, preferably over 50%, e.g. about Examples of aromatic hydrocarbonswhich may optionally be substituted with one or more halogen atoms,alkoxy or hydroxy radicals are: benzene and its derivatives, e.g.methyl-benzene, dimethylbenzene, ethylbenzene, isopropylbenzene,chlorobenzcne, methoxybenzene, hydroxybenzene, hydroxymethylbenzene,hydroxychlorobenzene, diphenyl and its derivatives, e.g. 2- or4-hydroxydiphenyl, and naphthalene and its dcrivatives, e.g. 1- or2-hydroxynaphtl1alene.

Examples of suitable sulphonation agents are: to sulphuric acid, 0 to65% oleum, chlorosulphonic acid, amidosulphonic acid, sulphur trioxideor sulphuryl chloride or mixtures of, e.g., 100% sulphuric acid andchlorosulphonic acid.

The sulphonation agent is advantageously used in an amount of from 1 to2 mol, preferably 1.2 to 1.7 mols, (calculated as 100% sulphuric acid)for every mole of the compound of Formula II). Evidently it is possibleto use greater quantities of the sulphonating agent, e.g. up

to about 10 moles per mol of compound of Formula II, as is the case inproducing benzene or naphthalene polysulphonic acids or dyestuffsulphonic acids (Fierz-David and Blangey, Grundlegende Operationen derFarbenchemie (1943) pages 138; 201 or 301); however, this use of largeamounts of sulphonating agent is designed to lead to a minimum ofsulphone formation and therefore offer no advantage for the productionof compounds of Formula I.

It is possible to effect the reaction in one stage, e.g. in a singletub, or in two or even three stages; the reaction, e.g., may be startedat room temperature and completed at about 220 C. It is advantageous toeffect first a sulphonation with 90 to 100% sulphuric acid, with to 65%oleum, with chlorosulphonic acid or with sulphur trioxide at an initialtemperature of 20, then rising to 150 C. and then to condense theresulting monoor polysulphonic acid at a temperature of from 150 to 220C., optionally in the presence of a condensation agent (e.g. 80 01 SOCIPCl or Zncl the condensation being either intercondensation or with afurther compound of Formula II or with an aromatic hydrocarbonoptionally substituted with alkoxy or hydroxy groups. Suitably thecondensation is effected in such a way that the entire sulphonation massor the sulphonic acid, after isolating it from the sulphonation agentand preferably drying, or its ammonium salt, if desired with theaddition of a further compound of Formula II or an aromatic hydrocarbonwhich may optionally be substituted with halogen, alkoxy or hydroxygroups, is heated to temperatures of from 150 to 190 C. at atmosphericpressure or preferably at reduced pressure. As the condensation resultsin the production of 1 mol of water per mol of sulphonic acid radical(which is converted to a sulphonyl radical) and this water may haveundesirable side effects, it should be removed from the reaction mixtureat once after it has been formed. In order to speed up to the utmostthis removal of water, the pressure is suitably reduced, e.g. to below20 mm. of Hg. This may be effected by continuously or stepwise reducingthe pressure to a final value of to mm. of Hg (water pump) or 1 to 20mm. of Hg, preferably 1 to 10 mm. of Hg, (vacuum pump). It is evidentlypossible to effect the condensation at a pressure which is more than 20mm. of Hg, e.g. 30, 50 or 100 mm. of Hg, but in this case the reactiontakes longer unless a correspondingly higher working temperature isused. Instead of reducing the pressure it is likewise possible tointroduce over or in the condensation mass a dry and inert gas stream(e.g. nitrogen or carbon dioxide), so as to remove the water in the formof water vapour, or to carry out the condensation in an inert organicmedium acting as an entrainment agent, e.g. dichlorobenzene,nitrobenzene, chloronaphthalene, or to use an entrainment agent and worksimultaneously at a reduced pressure.

The duration of the sulphonation depends on the specific compound of theFormula II used, the sulphonation agent used, the desired degree ofsulphonation and the sulphonation temperature and amounts to, e.g., 1-4hours at 100 C. using 1.5 mols of 100% sulphuric acid per mol ofdiphenyl oxide. By testing the solubility in water alone or in thepresence of an acid binding agent it is possible to follow easily thecourse of the sulphonation.

The duration of the condensation likewise depends on many factors, e.g.the temperature, the pressure and the degree of condensation. As acontrol test it is possible to measure the amount of water split off orthe total acid content of a sample of condensation mass, the differencebetween the acid content at the beginning and that at the end of thecondensation being a measure of how far the reaction has proceeded.

When the condensation products are insufiiciently water soluble or havean unsuitable afiinity for fibres, it is possible to after-sulphonatethem to impart to them the required solubility in Water or aflinity tofibres when they are used, e.g., as dyeing auxiliaries. For this purposethere may be suitably used as the sulphonation agent concentratedsulphuric acid, oleum or chlorosulphonic acid and working is effectedunder the conditions mentioned for the sulphonation, if necessary in thepresence of an organic solvent. The condensation products may be aftertreated with formaldehyde or a methylol radical containing connectingagent, e.g. dimethylol urea, polymethylol melamine, preferably usingalkaline or acid conditions.

In the resulting sulphones of the Formula I thefree sulphonic acidradicals may be neutralized with an ammonia solution and the resultingsolutions, if desired after filtering to clearness, may be evaporated todryness or dried in a jet drier or used as such.

Instead of the ammonia solution it is possible to neutralize with asodium, potassium, or lithium hydroxide solution, a sodium or potassiumcarbonate solution or, alternatively, the solid carbonates orbicarbonates of sodium, potassium or lithium. Further suitableneutralizing agents are magnesium oxide or carbonate, calcium oxide,hydroxide or carbonate, further solutions of water soluble amines, e.g.,methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine,diethanolamine, triethanolarnine, as well as the correspondingpropanolamines and hexamethylenetetramine.

The condensation products resulting by treatment with formaldehyde orwith a methylol radical containing connecting agent in alkaline mediummay be neutralized with sulphuric acid or another acid, e.g.hydrochloric, acetic, formic or also phosphoric acid or with an organicsulphonic acid (methane, benzene or 4-methylbenzene sulphonic acid),while in the case of treatment in acid medium with formaldehyde or withmethylol radicals containing connecting agents there may be used theabove bases.

The sulphones of Formula I and their above derivatives are very suitableas textile auxiliaries, especially for level dyeing polyamide fibresshowing stripes or rings on normal dyeing with anionic dyestuffs, asthey are able to regulate the absorption rate and the dye distributionof anionic dyestuffs in fibres to be dyed. However, they can likewise beused very successfully for dyeing in a uniform shade mixtures ofsynthetic polyamide fibres and elastomeric fibres on a basis ofpolyurethanes which are polycondensation products of diols anddi-isocyanates, e.g. of 1,4-butanediol and1,6-hexamethylenediisocyanate, or mixed condensation products ofpolyethers or polyesters with diisocyanates and diarnines or hydrazine[Ullmann Enzyklop'aidie der technischen Chemie, 14, 338-363, especially351-2 (1963)].

The term anionic dyestuffs designates dyestuffs which are capable offorming coloured anions in aqueous dye liquors, for example acid leveldyestuffs, milling dyestuflfs, 1:1- and 1:2 metal complex dyestuffs,chrome dyes, direct dyes and reactive dyes.

The conditions under which dyeing is effected are essentially thoseusual for the specific anionic dyestuff used e.g. temperatures of fromto 140 C., preferably to 130 C., an elevated pressure being used whenthe dyeing temperature exceeds C.; liquor ratios of 1:5 up to 1:200,preferably from 1:10 up to 1:100; pH values of from 2 to 8 depending onthe dyeing properties of the dyestuff used when the treatment of thefibres with the sulphone of the present invention is carried out in thedye bath itself.

However, treatment with the sulphone of the present invention maylikewise be effected before the actual dyeing and this at temperaturesof about 20 C. to 100 C., preferably at 50 to 100 C. under weakly acidconditions, e.g. in an acetic acid medium. The fibres treated in thisway may be removed from the liquor, rinsed with water, optionally driedand then brought into a freshly prepared dye bath and dyed therein, ordyed directly in the treatment bath after adding thereto to a dyestuffand optionally one or more dyeing assistants, for example salts, acids,metallizing agents and surface active agents.

The quantity of sulphone of the invention used will depend, inter alia,on the nature of the fibres to be dyed, the amount and structure of thedyestulf used for dyeing, the pH value of the dye bath, the dyeingtemperatre and the duration of the operatiton. This amount may varybetween 0.02 to 20% by weight, preferably 0.1 to by weight, based on thematerial to be dyed. In addition to the sulphone of the presentinvention, there may be added to the dye baths buffer substances, e.g.hexamethylenetetramine, disodiumphosphate, tetrasodiumpyrophosphate,urea or ammonium rhodanide. Optionally there may be added to the liquor,in addition to sulphone and dyestuff, one or more non-ionic, anionic orcationic capillary active compounds, providing they do not produceprecipitate with the dyestuff and the sulphone.

The sulphones of Formula I possess the great advantage that theypractically do not foam as do the known sulphonated diphenyl oxideswhich contain a long aliphatic chafn; furthermore, they are very gooddispersing agents in acid or neutral medium and also, in contrast toe.g. sodium dinaphthylmethanedisulphonate, in alkaline medium.

The dyeings which can be obtained in accordance with the dyeing examplesgiven hereinafter are level and of uniform shade, and otherwise possessthe good properties which are peculiar to the anionic dyestuffs used.

In the following examples parts and percentages are by Weight and thetemperatures are stated in degrees centrigrade. In the structuralformulae Ph is the phenyl or phenylene radical respectively, n is 1, 2or 3, and m is 1 or 2.

EXAMPLE 1 168 parts of diphenylene oxide (i.e. dibenzofuran) (1 mol)together with 147 parts of 100% sulphuric acid (1.5 mols) are heated for4 hours to 100. The temperature is subsequently increased during 2 hoursto 140 and condensing is first effected for 2 hours at 140 at a pressureof 13 mm. of Hg and then for a further 3 hours at 160 at a pressure of 3mm. of Hg. The resulting product has an acid content of 45S mvaL/ 100 g.of product (titrated against Congo red). While the melt is still hot itis removed from the reaction vessel and allowed to cool, whereby a solidcake results on solidification. The resulting light brown product may bepulverized and stored as such or stirred with an equal quantity ofwater, the resulting mass neutralized with 30% sodium hydroxide solutionand evaporated to dryness.

Instead of using a sodium hydroxide solution it is likewise possible touse the corresponding amount of ammonium hydroxide solution.

The light brown powdered sulphone has the following formula:

acne-Lace i EXAMPLE 2 184 parts of 3-hydroxy-diphenylene oxide of theformula 6 are used and working is first effected as described inExample 1. The melt is then kept at 180 at a pressure of 3 mm. of Hguntil the acid content amounts to 350 mval./ g. (titrated against Congored). Working up is effected in the manner described .in Example 1.

The resulting product has the following formula:

EXAMPLE 3 147 parts of 100% sulphuric acid are slowly added to 170 partsof diphenyl oxide and heated for 4 hours to 100. Subseqlently thepressure is reduced to 20 mm. of Hg and the temperature is raised during2 hours to 160. At this temperature condensation is effected for 4hours. The pressure is then reduced further to 3 mm. of Hg andcondensation is continued until a sample of the condensate has an acidcontent of 374 mval./ 100 g. of resin (titrated against Congo red). Thehot melt is removed from the reaction vessel and allowed to solidify.

The resulting light brown product can be pulverized and stored as suchor it is mixed with the same weight of water, neutralized withconcentrated ammonia solution and the solution is adjusted to a 40%content of active substance (calculated as ammonium salt).

The light brown powdered product has the followin formula:

EXAMPLE 4 246 parts of a yellow brown oil having a neutral reaction andcontaining phenoxy-diphenyl as the main constituent (the physicalproperties of this oil are density: 1.139, solidification point: 0,boiling point: 270350) together with 148 parts of 100% sulphuric acidare heated for 4 hours to 100. Subsequently the pressure is reduced to17 mm. of Hg and the temperature is increased to during 2 hours. Thepressure is then further 10W- ered to 2 mm. of Hg and the temperatureincreased to 15 0. Condensation is then effected until a sample of thecondensate has an acid content of 350 mvaL/ 100 g. of resin (titratedagainst Congo red).

The resulting sulphone is worked up in the manner described in Example3. It can likewise be isolated in the form of the sodium salt asdescribed in Example 1. It has equally good properties as the product ofExample 3.

The sulphone has the following formula:

EXAMPLE 5 Working is effected in the manner described in Example 3, butusing 127.5 parts of diphenyl oxide and 70.5 parts of hydroxybenzene andthe condensation is effected at and 3 mm. of Hg until the acid contenthas fallen to 355 mval./ 100 g. of product (titrated against Congo red).

The resulting product is a mixture of sulphones having the followingformulae:

By replacing the hydroxybenzene with the equivalent amount of 2-, 3- or4-methyl-l-hydroxybenzene or a technical mixture thereof, methylordimethylbenzene, methoxyor ethoxybenzene, naphthalene, 1- or2-hydroxynaphthalene similar products are obtained.

Sulphones with similar properties are also produced by using 170 partsof diphenyl oxide and 47 parts of hydroxybenzene or the equivalentamount of, e.g., a methyl-hydroxybenzene mixture, xylene or naphthalene.

Further sulphones of Formula I are produced in the same manner usingcorresponding compounds of the Formula II:

Acid content, Compound of Formula II: mval./100 g. (a) Diphenyl sulphide(186 parts) 375 (b) Mixture of 119 parts of diphenyl oxide and 74 partsof the oil used in Example 4 360 The compound (a) above has thefollowing formula:

EXAMPLE 6 117 parts (1.2 mols) of 100% sulphuric acid are slowly addedto 166 parts (1 mol) of a mixture of 26.5% diphenyl and 73.5% diphenyloxide. The mixture is first heated to 100 for 4 hours, the pressurereduced to 17 mm. of Hg and the temperature increased to 160 during 2hours. Condensation at this temperature is effected for 4 hours, thepressure is reduced to 3 mm. of Hg and the reaction temperature isincreased to 180. Condensation is then effected until a sample of thecondensate has an acid content of 348 mval./ 100 g. (titrated againstCongo red).

The sulphone is worked up in the manner described in Example 1 and is amixture corresponding to the following formulae:

Ii-n

il-n

and

EXAMPLE 7 170 parts (1 mol) of diphenyl oxide are placed into 245 (2.5mols) of 100% sulphuric acid and heated to 130 for 2 hours. The acidcontent of a sample then amounts to 755 mval./100 g. (titrated againstCongo red). The pressure is then lowered to 11 mm. of Hg and theresulting water is removed; the acid content then rises to 770 mval./100 g. The pressure is again allowed to rise to 760 mm. of Hg and 340parts (2 mols) of diphenyl oxide are added at 130 and the mixture isheated to 210; this is first kept for 2 hours at 210 and 760 mm. of Hgand then for a further hours at 210 and a pressure of 7 mm. of Hg,whereby a little unreacted diphenyl oxide distill distills off. Theresulting sulphone has an acid content of 170 mval./1-00 g. (titratedagainst Congo red) and is worked up in the manner described in Example1.

EXAMPLE 8 170 parts (1 mol) of diphenyl oxide are dissolved in parts ofacetic acid anhydride at room temperature. 98 parts of 100% sulphuricacid are added dropwise to this solution during about 20 minutes and thetemperature is allowed to rise to 95100, whereby the solution becomesprogressively darker. Further heating to is then effected for 1 hour andthe sulphonation mixture is poured into 750 parts of ice water. A smallamount of undissolved material is filtered off and the initially oilyfiltrate is subjected to water vapour distillation to remove excessdiphenyl oxide. The aqueous solution is then evaporated at a reducedpressure. The resulting residue, having an acid content of 535 mval./10Og., is heated to 160 at a pressure of 6 mm. of Hg until the acid contentis 355 mval./ 100 g., and working up as in Example 3 is effected.

EXAMPLE 9 174.5 parts (1.5 mols) of chlorosulphonic acid are addeddropwise, while cooling well and stirring, to 170 parts (1 mol) ofdiphenyl oxide during several hours, so that the temperature amounts toabout 30. The sulphonation takes place with strong hydrogen chlorideevolution. The mixture is then heated for 2 /2 hours to -140, the acidcontent amounting to 490 mval./100 g., then for several hours to at apressure of 5 mm. of Hg, the acid content thereby falling to 390rnval./100 g. (titrated against Congo red).

The resulting condensation product dissolves in water to give a clearsolution; it is worked up in accordance with the details of Example 1.

When the chlorosulphonic acid is replaced with 177 parts (1.9 molscalculated as 100% sulphuric acid) of oleum with about 27% S0 andworking up is otherwise elTected as described above, a similar watersoluble product results of which the acid content during thecondensation at reduced pressure falls from 590 mval./100 g. to 540mval./100 g.

EXAMPLE 1O 50 parts of acid resin produced according to Example 3 aremixed with 36 parts of 30% sodium hydroxide solution and condensed with4.5 parts of dimethylol urea at temperatures of 50-60 for about 6 hoursuntil a sample of the condensate is Water soluble. The excess of sodiumhydroxide is then neutralized with dilute sulphuric acid and the entirematerial is evaporated to dryness. A light brown water soluble powderresults.

EXAMPLE 11 50 parts of acid resin produced according to Example 3 aremade alkaline with 34 parts of 30% sodium hydroxide solution, 11 partsof 37% formaldehyde solution are added and condensation at temperaturesbetween 95 and 105 is efiected until formaldehyde odour is no longerdetectable. The sodium hydroxide excess is neutralized with dilutesulphuric acid and all the material is evaporated to dryness. A lightbrown water soluble powder results.

The products of Examples 7, 8 and 9 have a formula corresponding to thatof Example 3.

Dyeing Example (A) Yarns consisting of 50 parts of nylon 6.6 and 50parts of a spandex fibre Lycra (Ullmann 14 351 (1963) are dyed in 4000parts of a dye liquor containing the following additives:

0.25 part of sodium-1-amino-2-bromo-4-(4-methylphenylamino)-anthraquinone-2'-sulphonate 2 parts of 80% acetic acid and 2 parts ofsulphone described in Example 1 (in the form of the sodium salt).

The yarns are placed into the dye bath at 35 and heated during 40minutes to 95. Dyeing at this temperature is effected for 1 hour. Bothyarns are dyed level and with equal tint in a blue colour. A similarresult is obtained by using the sulphone of Example 6 instead of that ofExample 1.

Dyeing Example (B) 100 parts of a nylon 6.6 material which tends tobecome stripy on dyeing without special treatment, are dyed in 4000parts of a dye bath liquor containing 0.3 part of sodium 1 amino 4(4'-acetyla1ninophenylamino)- anthraquinone-Z-sulphonate, 4 parts of 85%formic acid and 2.5 parts of the solution of ammonium salt described inExample 3.

The material is put into the dye bath at 50, this is heated during 45minutes to 98 and kept for 1 hour at 98-100". The dyed material isremoved from the bath, rinsed with Water and dried. A greenish bluedyeing results which is level and free of stripes.

Although the present invention is described herein with particularreference to specific details, it is not intended that such detailsshall be regarded as limitations upon the scope of the invention exceptinsofar as included in the accompanying claims.

What is claimed is:

1. A compound selected from the group consisting of (1) a sulphone ofthe formula wherein m represents 1 or 2, n represents 1, 2 or 3, A and Aare the same or diflferent and each represents the residue of a compoundof the formula a)p 011 wherein each of Z and Z represents a. memberselected from the group consisting of hydrogen, chlorine, 1- to 3-carbon alkyl, 1- to 3-carbon alkoxy, hydroxy and phenyl, each of p and grepresents 1 or 2,

and Y represents a member selected from the group consisting ofhydrogen, NH alkali metal, alkaline earth metal and an amino groupcontaining one or more alkyl groups of 1 to 3 carbon atoms. 2. Acompound according to claim 1, in which the com pound of Formula II isdiphenyl oxide.

3. A compound according to claim 1, in which the compound of Formula IIis phenoxy-diphenyl.

References Cited UNITED STATES PATENTS 3,110,683 11/1963 Steinhayer eta1. 26-5l2 ALEX MAZEL, Primary Examiner B. I. DENTZ, Assistant ExaminerUS. Cl. X.R.

